JPS59152960A - Production of organic pigment containing inorganic powder as a nucleus - Google Patents

Abstract

PURPOSE:An organic compound is introduced onto an inorganic powder by mechanochemical reaction, then an organic pigment is synthesized on the powder utilizing the organic compound introduced to produce the titled pigment with high resistances to water, solvents and high duration. CONSTITUTION:An organic compound such as a benzene derivative is introduced on the surface of inorganic powder by utilizing mechanochemical reaction between an inorganic powder such as silica, alumina or aluminum hydroxide and an organic compound such as 4-aminobenzoic acid or 4-aminonaphthoic acid, e.g., by a mechanical operation such as grinding. Then the resultant organic compound is used to synthesize a dye or pigment on the surface of the inorganic particles, thus giving the objective pigment. EFFECT:Appropriate selection of inorganic powders, their particle sizes and mechanical energy permits the production of a pigment with desired opacifying strength and particle sizes.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an organic pigment using inorganic powder as the entire core, and its purpose is to appropriately select the type and particle size of the inorganic powder as the core. At the same time, by fully adjusting the strength of the applied mechanical energy, it is possible to manufacture pigments with arbitrary @shielding power and particle size, as well as to achieve excellent durability such as water resistance, solvent resistance, and anti-bleeding properties. The purpose is to manufacture pigments.

Conventionally, organic pigments generally have brighter colors than inorganic pigments, but have poor hiding power and are often transparent. Therefore, if an opaque organic pigment can be produced, a group of organic pigments that are bright in color and opaque will be obtained.

Furthermore, among organic pigments, aromatic condensed polycyclic pigments containing a petro atom, such as copper phthalonanine, quinacridone, and isoindolinone, generally have excellent water resistance, solvent resistance, heat resistance,
Although they have excellent properties such as weather resistance, azo pigments, which are in high demand for a wide range of organic pigments, have bright colors but have poor water resistance, surface solvent resistance, and surface bleed resistance. Many are inferior.

For example, insoluble azo pigments have poor surface solvent properties and ml bleed properties, and azo lake pigments and laked azo food colorants have extremely poor water resistance.

As shown above, azo pigments have bright colors, but many of them are inferior in other properties, and the reason for this is mainly due to the chemical structure of the pigment itself, but the color of the pigment powder is This is often caused by the particle state.

In other words, one of the reasons for the inferiority of these properties is grain 1 (2). The poor prognosis can also be mentioned.

Based on the above-mentioned viewpoints, the present inventors first developed a method for producing dyes, pigments, etc. on the surface of metal oxides by fully utilizing the surface chemical reaction between hydroxyl groups existing on the surface of metal oxides and organic compounds. By synthesizing organic dyes, the particle size and hiding power can be adjusted as desired. Furthermore, organic dyes synthesized on the surface of metal oxides are chemically bonded to metal oxides, making them water resistant, solvent resistant, He invented a method for producing an organic pigment with a metal oxide core, which has excellent properties such as bleed resistance (patent application No. 1329619, 1982), but as a result of further research, the present invention was developed. We have completed a method for producing organic pigments using inorganic powders.

The structure of the method for producing an organic pigment as an inorganic powder according to the present invention will be specifically explained below.

The manufacturing process according to the present invention utilizes a mechanochemical reaction between an inorganic powder and an organic compound such as a benzene derivative to completely introduce an organic compound such as a benzene derivative onto the inorganic powder.
The second step is to convert the introduced organic compound into an organic dye such as a dye or a pigment.

The first step is to perform a mechanochemical reaction by applying mechanical operations such as wet or dry grinding to a mixture of an inorganic powder that is insoluble or poorly soluble in water and an organic compound such as a benzene derivative or a naphthalene derivative. to chemically bond the inorganic powder and the organic compound.

In this mechanochemical reaction, a highly active new cross section is developed on the crushed surface of the inorganic powder through mechanical operations such as grinding, and at the same time, a reaction occurs between this new cross section and the coexisting organic compounds. The purpose is to chemically combine the inorganic powder and the organic compound. That is, by this mechanochemical reaction, a coarse organic compound chemically bonded to the inorganic powder is introduced onto the surface of the inorganic powder.

The hiding power and particle size of the organic pigment used as the whole inorganic powder obtained by the production method according to the present invention are determined by the type and particle size of the inorganic powder used here, as well as the strength of mechanical energy. Therefore, it is necessary to use an inorganic powder suitable for the purpose and at the same time adjust the strength of the mechanical energy.

As the core inorganic powder, most can be used as long as it is insoluble or poorly soluble in water, including metal oxides such as silica, alumina, titanium oxide, and zinc oxide, and metal hydroxides such as aluminum hydroxide. or carbonate salts such as calcium carbonate and calcium sulfate.

In addition, the organic compounds that can be used react with the new cross section of the inorganic powder generated by grinding, and react with the inorganic powder to the grooves that retain chemical bonds, which induce organic pigments such as dyes and pigments. Anything that can be used is acceptable, such as 4-aminobenzoic acid, 2-aminobenzoic acid, 4-amino-3-
Benzene derivatives such as nitrobenzoic acid, 4-amino-1-
Naphthalene derivatives such as 7-toic acid can be used.

Next, the application of mechanical energy differs depending on the type and nature of the inorganic powder used, the degree of particle scraping of the target object, etc., but in general, it is possible to apply mechanical energy using a commonly used ball mill or A grinder or mixer such as a grinder is sufficient.

This mechanical operation must not decompose the organic compounds coexisting with the inorganic powder to such an extent that they cannot be converted into organic pigments such as dyes and pigments in the second step.

Therefore, from this point of view as well, it is appropriate to apply mechanical energy by grinding using a ball mill, lightning crusher, or the like.

The second step is the total synthesis of organic pigments such as dyes and pigments based on the organic compounds such as benzene derivatives introduced onto the surface of the inorganic powder in the first step. It is possible to produce all organic pigments such as dyes and pigments that can be derived from organic compounds while remaining in a chemically bonded state with inorganic powder.

Hereinafter, this invention will be explained by giving examples.

Example 1 (1) A mixture of 200y of γ-alumina and 20y of 4-aminobenzoic acid manufactured by Merck was dry-milled using an all-magnetic ball mill, and 4-aminobenzoic acid was completely coated on the surface of the γ-alumina particles. It is chemically bonded as an aluminum salt of 4-aminobenzoic acid and introduced in the t-plane.

＼ After the grinding process, take out the contents and wash thoroughly with acetone.
After vacuum drying at 50°C, lightly crush it in a mortar.

As a result of carbon elemental analysis, the amount of 4-aminobenzoyloxo groups introduced was 3.79% with a carbon content of 52. The Polmir used has an internal volume of 4500 cm3 and an internal diameter of 1.
7.5cm, and the rotational speed is Nmax = 42. 73 km, which is approximately 72% of Nmax calculated from inclusive C.
And so.

However, Nmax is the limit rotational speed, and D is the inner diameter of the mill.

The ball insertion rate is approximately 30% in actual volume per mill volume.
And so.

(2) 2 m o/! /l salt @250ml1k5℃
After cooling and adding sample 20y obtained in (1) while stirring, 2 moI! Sodium nitrite aqueous solution of A 50ml
1k, and diazotize it by adding it while being careful not to leak liquid exceeding 10oC.

(3) 2 moe/f contained in 2-naphthol 28.8y'
250ml of sodium hydroxide aqueous solution! Cool to 5°C, stir, and gradually add the diazotized suspension from (2) while being careful not to let the liquid temperature rise above 10°C.
Coupling is performed by leaving the mixture for 10 minutes while stirring.

However, the pH of this reaction must be adjusted with dilute hydrochloric acid to make it slightly alkaline.
Do this while adjusting.

After coupling, add 250 ml of acetone to this suspension.
m1k was added to dissolve excess organic matter not bonded to γ-alumina, and after filtration, the P solution was washed with water until it became almost neutral, and then washed with acetone and vacuum-dried at 50 °C. A bright red organic pigment powder having almost the same color as Dye Sudan 1 was obtained by crushing it with a milk wasp to form γ-alumina cores.

The surface of this pigment is as follows.

This red pigment is made by chemically bonding an organic dye with a structure similar to that of the red dye Sudan 1 on γ-alumina, but the amount of organic dye bonded to the r-alumina surface was determined by analysis. As a result, the carbon content was 7.72%.

The pigment thus obtained is a bright red pigment that has excellent water resistance, solvent resistance, and bleeding resistance, and exhibits a hiding power of 54 CmZy as measured with a Hund cryptometer.

Example 2 In Example 1, 2-naphthol was used as a camping agent, but 3-carboxy-1-(4'-sulfophenyl)-5-pyrazolone (monosodium salt) was used instead of 2-naphthol. An organic pigment with excellent water resistance and anti-bleeding properties was obtained by coupling with the γ-alumina core, which had a bright yellow color almost the same as Yellow No. 4, which is widely used as a food coloring.

However, in Example 1, 2 mol/I containing 2-naphthol 2: gr8 yk! 250ml of sodium hydroxide aqueous solution
In this example, coupling agent 6.1. Coupling was carried out in 350 ml of an aqueous sodium hydroxide solution.

The surface structure of the pigment thus obtained is as follows.

γ Hiroshi Example 3 Zinc oxide (manufactured by Kanto Kagaku Co., Ltd.) was used in place of γ-alumina, and zinc oxide with excellent water resistance, solvent resistance, bleed resistance, etc. was prepared using the same method as in Example 1. Obtained an opaque organic pigment with great hiding power for a bright red core.

Example 4 A red color similar to toluidine red (Permanent Red 4R) was prepared in exactly the same manner as in Example 1 using 4-amino-3-nitrobenzoic acid instead of 4-ami7benzoic acid. An organic pigment containing γ-alumina as a core and having extremely excellent solvent resistance and bleed resistance was obtained. The measurement result of the hiding power was 65 Cm/y.

The surface structure of this red pigment is as follows.

Example 5 In the same manner as in Example 1, γ-alumina 20 manufactured by Merck & Co., Ltd.
(ly and 20y of 4-amine-3-nitrobenzoic acid
The mixture was thoroughly dry-milled and then diazotized,
Contains acetoacetanilide 35.4y'C'1mne/
Coupling in 250 mg of sodium hydroxide aqueous solution produces a yellow γ- color that is almost the same color as Hansa Yellow 5G.
An organic pigment containing alumina as a core was obtained.

This pigment has much better water resistance and bleed resistance than Hump Yellow 5G.

Its surface structure is as follows.

H3 Example 6 Instead of 2-naphthol in Example 1, 2-hydroxy-
Using 3-naphthoic acid and the same method as in Example 1, a red γ-alumina-based pigment similar to Brilliant Carmine 6B was obtained. However, Kampling is 2-
350 ml of 2 ml/l sodium hydroxide aqueous solution containing 37.6 fil f of hydroquine-3-naphthoic acid
I used it. Brilliant Carmine 6B has poor water resistance, but this pigment has extremely good water resistance.

The surface structure of this pigment is as follows.

Example 7 Zinc oxide (manufactured by Kanto Kagaku Co., Ltd.) 2 was prepared in the same manner as in Example 1.
A mixture of 00y and 20y of 4-amino-3-nitrobenzoic acid was completely dry-milled and then diazotized, and a mixture containing 52.6y of 2-hydroquine-3-naphthoic acid anilide was prepared.
moff/I! An opaque organic pigment containing zinc oxide as a core was obtained by compounding in 250 ml of an aqueous sodium hydroxide solution with a color similar to toluidine maroon (reddish brown).

Although toluidine maroon has a drawback in solvent resistance, this pigment has excellent solvent resistance.

The surface structure of this pigment is as follows.

Patent applicant Kinki University Educational Corporation 7. , Patent Attorney Ogawa-Omi 1 Procedural amendment March 1, 1980 Patent application filed on February 21, 1980 Application No. 2, 1982 Title of invention Organic pigments with inorganic powder as the core Manufacturing method 3, relationship with the case of the person making the amendment Patent applicant name Educational corporation Kinki University 4° Agent 542 Telephone (06) 262-0500 (2)
) Certification submission form 8 under Article 30, Paragraph 4 of the % Permission Act Contents of the amendment (1) Detailed explanation of the invention in the specification column ii) In the 5th line of page 6 of the specification, the words "mechanical energy" have been added. , mechanical energy, is corrected.

(Note) In the 6th line of the main text on page 7, correct the word "pormir" to "ball mill."

c) Page 9, line 3 Chemical structural formula and correct the combined sign.

2) Structural formula on page 12

Claims (1)

[Claims] Utilizing a mechanochemical reaction between an inorganic powder and an organic compound, an organic compound such as a benzene derivative is introduced into the inorganic powder, and the introduced organic compound is converted into a base. A method for producing organic pigments using inorganic powder as a core, which is characterized by total synthesis of organic pigments such as dyes and pigments on the surface of inorganic objects.